Process of treating metallic salt solutions



Jan.. 2l, 936. p (y,l RICH PROCESS 0F TREATING METALLIC SALT soLUTIoNsFiled June l1, 1934 www mm mm, @my mm@ Q @$5 mkomu L .E6 @wwwa wwwww wm.m. Qwm m N A N N m .wm .w\\ L Qm,\ QMQOQU l QMLR .Q uwk uthw L, m,

ll. Q wmks INVENTOR FWZ/L. C'. /C/ BY v. waz/WW SW ATTORNEY y loFatented Jan. 21, 1936 PROCESS F TREATING METALLIC :SALT

SOLUTIONS -Paul' C. vltich, Los `Angeles,JCalif.,f assigner to VaporyTreating' Processes, Inc.,1lLos Angeles, I Calif., .ancorporation of.'.California Application June1 1 1, 1934,' .SriallNiLf 3,0,145

14 Claims.

:This invention relates to revi.virlcation.ofme-v tallic salt solutionsV.associated with-impurities which have Abeen :used in .purifying-fi andrefining hydrocarbon oil by contact therewith, and `is especiallyadapted for. revivifying; such-lsalt7V solutionsiafterfuse astdescribedinU.; S., Patent #1,809,170, issued,.to.Arthur .LachmanJune v9,

,1931, Process of refining hydrocarbon oils, which describes, thepurificationsand refining of hydrocarbon oils Vinfvapor` phase, usi-ngywater solutions oimetallic .saltsorsmixtures thereof, such as thechloride, ybromide,io dide, sulphate,- nitrate,Y etc., ofy zin c,copper,cadmium, mercury, iron, chromanganesa, aluminum,v `nickel and cobalt,

,which areheavy metal salts.

,In general, `this inventionz'maybeusedvftorevivify, for reuse. anyof.the metallicA salt solutions which have y.loeenused for purifyingaandrening hydrocarbon oilsloy any liquidforlvapor phase ,method known,.inathe art, and- :which may also ,includeVinraddition,to vtheabovenamed salts, salt solutions .of ,magnesium, calcium, ammonia,oxyvchlorides,:mixed base oxyhalides and double-salts.

Metallic-salt.r solutions when ,used ,to 'refine hydrocarbonoilsrsuch asgasoline;-naphtha,or other .like hydrocarbonoilv,distillatesbyzliquid orvapor. ,.phaseamethods, take upl impurities, notablyoil l salt of`thesolution 4may be converted tothe corresponding sulphide, thisIconversionto the sulphide depending upon-the, reactive sulphur contentrvof the Ioil stockbeing treated.

In the usecf `water, solutionsrof metallicsalts, such, fon, example, .as.concentrated solutions of zinc chloride, for purifying and stabilizing.gasoline stocks .orotherldistillates by contact therewith at ,elevatedtemperatures, I hayefdiscovered that the compcundswhich gradually renderinert the zinc chloride in usearecomposed largely of .nitrogen base,saltS, `such as pyridine hydrocarbons `orother like. nitrogenbaseacidsalts, and resinous compounds, particularly when gasoline stocksderived from cracked. petrolemncil products are treated. I believe thatlthe resinous compounds are produced duringthe treatment of gasolinestock with metallic. saltA solutions, at elevatedk temperatures bypolymerization of acetylene, diolene andlikehydrocarbons contained inthe stock,.while thenitrogen compoundsare. .usu-

yconcentratedzinc chloride solution, at-.temperatures ranging Vfromabout300 to 450F. or lower, ..hydr.olysis., of the zinc chloride; is effectedto a limited extent, with .the formation, usually,.-0I .small :amountsof zinc oxychloridesand the lib-- eration ,of hydrochloric acid, whichreacts in. part .with ,thehitrogenbase compounds, formingcorrespondingv` hydrochloric.. acid .salt which is dissolved loyf` theZincgchloride solution. v

Now, I have. discovered that if theseused me tallic -salt solutions. betreated with a. metal base, .-a rnetalv base ,or oxide suspendedI in-water, a ,soluble .metalrbase or, oxide dissolyedinwaten and/or, ametal base or oxide suspendedlinoil, such,..for .example,-as the oxideorhydroxide of ,Ithemetal in themetal salt solution, which may bezincoxideonhydroxida and/or the oxide ror `hydroxideof any ofthe metalsLheretoforeenumerated, `the lnitrogen base impurities contained thereinmaybe separated as an oily-liquidby differentialgravities thereof, andthe solution revivied; `alsothat the metal base is converted tothecorresponding metal salt. -The chemical reaction. involved in thisrevivication operation when zinc oxide 'is` us ed may be. expressed asykfollows:

4.An objectA ofthe invention is .torevivify metallic ,salt solutionswhich havebeen used to purify and rene .hydrocarbon oil, so that therevivified metallic salt solution may be continuously vused for f,,tlie, .fur th.ery purication and rening of hydro- .,carbon oils.

Another object of the invention is to revivifx .metallic saltfsolutionswhich have been used to purify and refine hydrocarbon oils, with anoxide or `hydroxide of a metal, whereby4 the original activepower of thesalt solutionmay be substanntially restored, and the oxide orhydroxideof the metal employed. for the Vrevivication converted intojametal saltwhich is also suitable for use in combination with therevivied solution to purify ,and rene hydrocarbon oil.

Another object of the invention is torecover Anitrogen,basehydrocarbonsin commercially valuable form.

l 1 have, further' discovered that the restoring of the active power ofthe salt solutions, the recovery of the impurities in commerciallyvaluable form, and the conversion of the oxide or hydroxide employed forthe revivication into salt solutions suitable for purifying and refininghydrocarbon oil, may be most economically conducted in apparatus whichwill be herein described. Reference is therefore made to theaccompanying drawing, which illustrates diagrammatically the preferredapparatus in which the process may be conducted.

In the drawing, I represents generally a pipe for conveying spentmetallic salt solution, which has been used for purifying and refininghydrocarbon oils, from a source of supply to lter press 2. A containeror tank 4 is stationed below filter press 2 to hold the metal sulphideseparated from the spent metallic salt solution. Pipe 3 connects theoutlet of filter press' 2 to settling tank 5. Pipe 6, controlled byValve 1, connects settling tank 5 at the bottom to a tank 8 for holdingseparated oil. A pipe IU, controlled by valve 9, connects tank 8 to astorage not shown.

A branch pipe I2, controlled by valve II, connects pipe 6 to the inletof pump I3. Pipe I4 connects the discharge side of pump I3 to treatingtank I5.. A mechanically operated mixer I8 of any well known typ-e isstationed within tank I5. Pipe I6, controlled by valve Il, connectstreating tank I5 at thetop to a source of water supply. Pipe 2|,controlled by valve 22, connects treating tank I5 at the top to a sourceof metallic oxide or hydroxide, and/or metallic oxide or hydroxidedissolved or suspended in water or an oil.

Pipe 23, controlled by valve 24, connects treating tank I5 at the bottomto the inlet of pump 25. Pipe 26, controlled by valves 21 and 4D,connects the discharge side of pump 25 to tank 31, which is used to holdthe nitrogen base oils separated in the process, and which may beintermittently transferred to other storage through pipe 38, controlledby Valve 39. A branch pipe 28, controlled by valve 29, connects pipe 26to a heater or cooler 30. Pipe 3| connects heater or cooler 3D totreating tank I5 near the top. A branch pipe 32, controlled by valve 33,connects pipe 25 to revivifled salt solution tank 34. From tank 34 therevivified salt solution may be transferred through pipe 35, controlledby valve 3B, to other storage or a treater and used thereafter fortreating hydrocarbon oils of any type.

The preferred process as carried out in the apparatus just described isasfollows:

A water solution of metallic salt or salts, such as a substantiallyconcentrated solution of zinc chloride or other salts, which have beenused for purifying hydrocarbon oils and contain impurities, such asmetal sulphides, emulsied oil and nitrogen base salts, as heretoforedescribed, is caused to flow through pipe I under pressure, and thenthrough filter press 2 wherein the flocculent solid impurities areseparated from the liquid contents and the emulsied oil liberated. Theflocculent Asolid impurities, consisting principally of metal sulphides,which collect on the lter plates of lter press 2, may be intermittentlyremoved and dropped into metal sulphide tank 4. These metal sulphideswhich are separated from the salt solution to be revivied may beconveyed from tank 4 to other apparatus and reconverted to the metallicsalt solution for further use by methods known in the art, such, forexample, as roasting in the presence of air and thereafter treating themetal oxide formed with water solutions of hydrochloric acid or othermineral acids.

The filtered salt solution, containing the libyerated oil and nitrogenbase salts, passes from filter press 2 through pipe 3, and then intosettling tank 5 wherein the liberated oil collects, forming a top layer,and is separated from the salt solution containing the nitrogen basesalts. rlhe salt solution, containing the nitrogen base salts insolution, is conveyed from tank 5 through pipe S, pipe I2 and into theinlet side of pump I3, with valve II open and valve 'l closed. Pump I3discharges the salt solution containing the dissolved nitrogen basesalts through pipe I4 and intotreating Ytank I5. After discharging allthe salt solution or bottom layer from tank 5 into tank l5, theremainder comprising the liberated oil is transferred from tank 5 intoseparated oil tank 8 through pipe 6, with valve 1 open and valve IIclosed. The separated oil which is collected in tank 8 may be conveyedto other storage through pipe I0, controlled by valve 9, and thereafterused for purposes known in the art.

The salt solution containing the nitrogen base salts in solution, intreating tank I5, is commingled with the necessary amount of a metallicbase, such as zinc oxide, which may be suspended in a uid such as water,or an oil which is a solvent of the nitrogen bases. The metallic base,suspended in water or in a solvent oil, may be introduced into treatingtank I5 through pipe 2|, controlled by valve 22, and/or the metallicbase in a comminuted solid state may be introduced directly intotreating tank I5 without the employment of a fluid suspension medium, inwhich case a mechanical conveyor may be used and water introduced-intotreating tank I5 through pipe I6, controlled by valve Il, to dilute themetallic salt solution to any required degree in order to facilitate theseparation of the liberated nitrogen bases and form a top layer abovethe salt solution. It is preferred that the quantity of water used todilute the salt solution be regulated so that the gravity of theresultant salt f solution will be greater than the liberated nitrogenbases, in order that the nitrogen base oils will form as a top layer.

After the required amdunt of metallic base andV water have beenintroduced into treating tank I5, containing the salt solution to berevivied, agitation and commingling of the metallic base with the saltsolution is effected by operating mechanical stirrer I8. Also,preferably, the

mixture o'f the metal base and salt solution is heated to a temperatureof about 150 F., more or less, in order to facilitate the chemicalreaction between the base and the nitrogen base salts contained in thesolution. This heating operation may be carried out by opening valves24- and 29 and operating pump 25 with valve 2l closed, whereby themixture is caused to circulate, passing from the bottom of tank I5through pipe 23, pipe 26, pipe 28, heater 39, pipe 3|, and then backinto treating tank I5 near the top. After the mixture of the metallicbase and salt solutio'n has been commingled and heated or cooled to therequired degree, and a substantially complete liberation of the nitrogenbases has been effected, the operation of mechanical stirrer IB and pump25 is discontinued.

After Standing and settling, the liberated nitrogen bases separate as anoily-liquid from the treated salt solution, forming a top layer.revivified salt solution is separated from the niiii) The

@maar into revivied salt solution tank 34, by operating pump' withvalves 24, 2l and 33 open and valves 29 and 40 closed, after which thetop layer oi nitrogen base oils is Withdrawn into tank 3l by closingvalve 33 and opening valve 40.

The revivied salt solution contained in tank 34 may be transferred toother storage through pipe 35, controlled by valve 3E, and thereafteremployed for the further treatment of hydrocarbon oil, either with orwithout concentration,

and/or withthe further addition of salt solution thereto. The nitrogenbase oils collected in tank 31 may be Withdrawn to other storage throughpipe 38, controlled by valve 39, and thereafter used for purposes knownin the art.

The quantity of metal base used to revivify metallic salt solutionswhich have been used to rene petroleum oils may vary through a Widerange, depending upon the per cent of nitrogen base salts contained inthe solution. As a specic example, 1000 gallons of a concentrated Watersolution of zinc chloride containing per cent of organic nitrogen bases,which had been used to treat gasoline stock produced by cracking highboiling California petroleum oil stock, required 300 pounds of dry zincoxide and 700 gallons of Water to liberate and separate the nitrogenbases contained therein, and produce a usable or re- `viviiied zincchloride solution.

While the process herein described is Well adapted for carrying out theobjects of the present invention, various modications and changes in thetreatment may be made to suit any type of contaminated salt solutionWithout departing from the spirit of the invention, and the inventionincludes all such modications and changes as appear Within the scope ofthe appended claims.

I claim:

1. A process of revivifying used Water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil with a Water solution ofmetal salt at temperatures ranging from about 300 to 450 F., comprising,commingling the used salt solution with a metallic base and thenseparating the liberated constituents from reviviled salt solution.

2. A process of revivifying used Water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil With a Water solution ofmetal salt at temperatures ranging from about 300 yto 450 F., as inclaim 1, in which the metallic base is an oxide of a metal.

3. A process of revivifying used water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil with a water solution ofmetal salt at temperatures ranging from about 300 to 450 F., as in claim1, in which the metallic base is a hydroxide of a metal.

4. A process o'f revivifying used water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil with a Water solution ofmetal salt at temperatures ranging from about 300 to 450 F., as in claim1, in which the metallic base is an oxide of the metal of the metal saltsolution.

5. A process of revivifying used Water solutions of heavy metal salts,containing nitrogen bases 23 and other organic v'extracted 'constituentslresulting :from the treatment of hydrocarbon oil with `a Watersolutionof metal salt at temperatures ranging from about 300-to 450 F.,as in claiml, in which the metallic base is Zinc oxide.

6. A process of revivifying used Water solutions of Yheavy metal salts,containing nitrogen bases and other organic extracted constituentsresult- Vling from the treatment of hydrocarbon oil with a Watersolution ofY metal salt at temperatures ranging from about 300 to 450F., as in claim l, in which the separated constituents are composedprincipally of nitrogen base compounds.

7. A process of revivifying used Water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil with a Water solution ofmetal salt at temperatures ranging from about 300 to 450 F., comprising,commingling the used salt solution 'with a metallic base suspended inWater, thereby converting the metallic base into a metallic salt, andthen separating the liberated constituents from reviviled salt solution,containing the metallic salt formed from the metallic base dissolvedtherein.

8. A processof revivifying used water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil with a Water solution ofmetal salt at temperatures ranging from about 300 to 450 F., as in claim7, in which the commingled mixture of salt solution and metallic base isheated.

9. A process of revivifying used Water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydroarbon oil With a Water solution ofmetal salt at temperatures ranging from'about 300 to 450 F., comprising,commingling the used salt solution with a metallic base dissolved inwater, and then separating the liberated constituents from reviviiedsalt solution.

10. A process Vof revivifying used Water solutions of heavy metal salts,containing extracted constituents and nitrogen base acid salts resultingfrom the treatment of hydrocarbon oil with a Water solution of metalsalt at temperatures ranging from about 300 to 450 F., comprising,

commingling the used salt solution with a metallic base and water,heating the commingled mixture to an optimum temperature to cause achemical reaction between the nitrogen base acid salt and the addedmetallic base, and then separating the liberated nitrogen base constituents from revivied salt solution.

l1. A process of revivifying used Water solutions of heavy metal salts,containing extracted constituents and nitrogen base acid salts resultingfrom the treatment of hydrocarbon oil with a Water solution of metalsalt at temperatures ranging from about 300 to 450 F., as in claim 10,in Which the amount of Water added along with the metallic base isregulated so as to produce revivified salt solutionhaving a greaterdensity than the liberated organic base constituents.

1'2. A process of revivifying used Water solutions of heavy metal salts,containing nitrogen bases and other organic extracted constituentsresulting from the treatment of hydrocarbon oil With a Water solution ofmetal salt at temperatures ranging from about 300 to 450 F., comprising,commingling the used salt solution with a metallic base suspended in anoil which is a solvent of the constituents to be separated, therebyconverting the metallic base into a metallic salt, and then separatingthe liberated constituents, dissolved in the oil from revivied saltsolution.

13. In the process of revivifying used Water solutions of heavy metalsalts, containing nitrogen bases and other organic extractedconstituents resulting from the treatment of hydrocarbon oil with aWater solution of metal salt at temperatures ranging from about 300 to450 F., the step which comprises, neutralizing the ex,- tractedconstituents with a base, and then separating the liberated constituentsfrom the salt solution.

14. A process of revivifying used water solutions of heavy metal salts,containing metal sulphides, nitrogen bases and other extractedconstituents resulting from the treatment of hydrocarbon oil with aWater solution of metal salt at temperatures ranging from about 300 to450 F., comprising, separating the metallic sulphildes and comminglingthe resultant salt solution with a metallic base, and nally separatingthe liberated constituents from the salt solution.

PAUL C. RICH.

CERTIFICATE OF CORRECTION.

Patent No. 2,028,475. January 2l, 1936.

PAUL C. RICH.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 3,first column, lines 42, 5l, 59, 67 and 75, claims l, 2, 3, 4 and 5respectively; same page, second column, lines 7, l5, 28, 56, 46, 59 and69, claims 6, 7, 8, 9, lO, ll and l2 respectively; page 4, first column,line 7, claim l5; and same page, second column, line 4, claim 14, strikeout the Word "heavy"; and that the said Letters Patent should be readwith these corrections therein that the same may conform to the recordof the case in the Patent Office.

Signed and sealed this 7th day of April, A. D. 1936.

Leslie Frazer (Seal) Acting Commissioner of Patents.

